Compatible anionic-catonic surfactant compositions

ABSTRACT

Novel surfactant compositions comprising an anionic surfactant and certain cationic surfactants compatible with same and in the form of quaternary ammonium compounds containing polyoxypropylene groups, said compositions exhibiting imprsved foam and solubilizing characteristics.

O United States Patent 1151 3,668,136 Barker June 6, 1972 1541 COMPATIBLE ANIONIC-CATONIC 3,141,905 7/1964 Longley ..260/567.6 SURFACTANT COMPOSITIONS 3,155,591 11/1964 Hilfer 424/70 3,325,414 6/1967 lnamorato .....252/137 [72] Bark", Lawn- 3,345,300 10/1967 Speel ..252/547 [73] Assignee: Witco Chemical Corporation, New York,

FOREIGN PATENTS OR APPLICATIONS [22] Filed: July 7, 1969 873,214 7/1961 Great Britain 252/8.75 [21] Appl. No.: 839,698

Primary Examiner-Leon D. Rosdol 52 U.S. c1 ..252/117, 252/355, 252/528,

H 2 7 Attorney-Wallenstcin, Spangenbcrg, Hattis and Strampel [51] .Int.Cl. ..C11d9/46,C11d1/65 [58] Field ofSearch ..252 117, 152, 355 ABSTRACT Novel surfactant compositions comprising an anionic surfac- [56] Rderences Cited tant and certain cationic surfactants compatible with same UNITED STATES PATENTS and in the form of quaternary ammonium compounds containing polyoxypropylene groups, said compositions exhibiting 2,734,830 ,2/1956 Hagge et a1. ,.l 17/47 imprsved f and Solubilizing h i fi 3,123,640 3/1964 Langley ..260/567.6 3,123,641 3/1964 Longley ..260/567.6 20 Claims, N0 Drawings COMPATIBLE ANlONlC-CATONIC SURFACTANT COMPOSITIONS This invention relates to novel compositions of matter com prising mixtures of cationic surfactants of specific structure and anionic surfactants generally, the compositions having unique surface active properties in aqueous solution. More specifically this invention relates to mutually compatible mixtures of anionic surfactants and cationic detergents comprising quaternary ammonium compounds having a polyoxyalkylene group linked to the nitrogen.

It is well known in the art that, generally speaking, cationic and anionic surfactants are incompatible in the same solution, both the cationic and anionic ingredients losing their surface active properties by virtue of interaction between the negatively charged hydrophobic group of the anionic surfactant and the positively charged hydrophobic group of cationic surfactant. The usual effect of such interaction is the elimination of the surface active properties of both materials.

It has, however, heretofore been known, as shown in U.S. Pat. No. 3,345,300, to admix cationic surfactants having a quaternary ammonium radical and a hydrophobic hydrocarbon group as, for instance, cetyldimethylethylammonium chloride, with certain specific types of anionic surfactants or detergents to produce compositions which, when added to water or aqueous media, are mutually compatible and do not interact to render their surfactant or detergent properties ineffectual. The specific types of anionic surfactants or detergents which are disclosed in said patent as possessing the foregoing compatibility with said cationic surfactants are mono-alkali metal salts of polybasic carboxylic acid mono-esters of the terminal alkylol group of a poly-oxyalkylated organic compound containing a hydrophobic hydrocarbon radical on the opposite end of the poly-oxyalkylene chain which contains from about two to 20 oxyalkylene units having from two to three carbon atoms per unit, the said hydrophobic hydrocarbon radical containing from eight to about 21 carbon atoms.

When cationic surfactants having a quaternary ammonium radical and a hydrophobic hydrocarbon group, as, for instance, cetyldimethylethylammonium chloride, or other cationic surfactants disclosed in the aforesaid U.S. Pat. No. 3,345,300, are admixed with numerous other anionic surfactants or detergents, such as, and particularly, those of the sulfate, sulfonate and phosphate ester types, such as sodium lauryl sulfate, sodium salts of sulfated higher fatty acid monoglycerides, dodecylbenzene sodium sulfonate, and sodium salts of phosphate esters of ethoxylated long chain alcohols and sodium salts of phosphate esters of ethoxylated long chain alkylphenols, incompatibility occurs in aqueous media and surfactant activity is effectively destroyed, precipitation usually occurring. Note, for instance, column 10, last two lines, and column 11, lines 18 of said U.S. Pat. No. 3,345,300. See, also, U.S. Pat. No. 2,213,477.

It has been discovered, suprisingly, that when certain particular types of cationic surfactants, hereafter described in detail, are admixed with anionic surfactants generally, and particularly where the anionic surfactants are of the sulfate, sulfonate and phosphate ester types, the resulting compositions are characterized by excellent compatibility in aqueous media and improved surface active characteristics, particularly with regard to foam boosting and stabilization, viscosity and solubilization in high-solid compositions. These novel cationic surfactant-anionic surfactant compositions are especially suitable for use in cosmetic detergent formulations such as shampoos, body detergents, facial cleansers, bubble baths and the like because of the foam boosting and stabilization effect and the solubilization of germicidal ingredients such as hexachlorophene without the need for addition of inactive ingredients such as ethylene glycols or propylene glycols which are generally used for such purposes. In addition, in the novel compositions of the present invention, the particular types of cationic surfactants which are utilized offer a distinct ad vantage over the commonly employed fatty amide and alkanolamide foam boosters and stabilizers which tend to build up viscosity, whereas said cationic surfactants function, in

among other ways, as viscosity reducing agents, thus offering, in the compositions of this invention, the highly desirable feature of simultaneously building foam and reducing viscosity.

The particular types of cationic surfactants which have been discovered to be useful in the compositions of the present invention are shown in U.S. Pat. Nos. 3,123,640; 3,123,641; 3,141,905 and 3,155,591, the disclosures of which patents in relation to said cationic surfactants are herewith incorporated into the present specification by reference.

Various of the cationic quaternary ammonium compounds, disclosed in the aforesaid U.S. Pats. Nos. 3,123,640; 3,123,641; 3,141,905 and 3,155,591, are represented by the formula wherein R is an alkyl radical containing from one to three carbon atoms, and more particularly from one to two carbon atoms, R, is an alkyl radical containing from one to three carbon atoms, and compounds wherein R and R, are joined together to form with the N atom a member of the group consisting of piperidine, methyl piperidine and pyrrolidine;

where R, is an alkyl radical containing from one to four carbon atoms, n is a number up to and including 60, the total number of carbon atoms in R being at least 18; R is a member selected from the group consisting of 1) alkyl and alkenyl radicals containing not more than four carbon atoms, and (2) benzene; methyl benzenes; ethyl benzenes;

and their methyl and ethyl nuclearly substituted derivatives; and the mono-halo and mononitro nuclearly substituted derivatives of the foregoing; and A is an innocuous anion. It may be noted that, in the above formula, in place of piperidine, methyl piperidine and pyrrolidine, other heterocyclic compounds can be used in which the R and R, radicals are joined together with the N atom, as, for instance, ethyl piperidine, isopropyl piperidine, methyl pyrrolidine, ethyl pyrrolidone, isopropyl pyrrolidone, and indole. Similarly, R may comprise other radicals over and above those identified above, as, for instance, isopropyl benzene, naphthalene, methyl naphthalenes and isopropyl naphthalene.

Again, as disclosed in the aforesaid patents showing the particular types of quaternary ammonium compounds which, according to the present invention, have been found to possess utility for the purposes of this invention, there are those derived from low molecular weight alkyl secondary amines and cyclic amines which can be represented by the formula wherein R is an alkyl radical containing from one to three and more particularly from one to two carbon atoms, R, is an alkyl radical containing from one to three carbon atoms, or

may be a radical of a cyclic amine containing not more than six carbon atoms, R is a polyoxyalkylene radical containing at least 18 carbon atoms and derived from an a-epoxide containing at least three carbon atoms, especially propyleneoxide. In those cases where R is derived from propyleneoxide, there will be at least six of such propyleneoxide groups in R and, more particularly, it is desirable that R contain from 8 to 30 oxypropylene groups. Where R is derived from a-epoxides containing more than three carbon atoms, a lesser number of such oxyalkylene groups can be present, subject to the limitation of R, containing at least 1 8 atoms. R; is advantageously a lower alkyl or alkenyl radical containing from one to four carbon atoms; or a lower aliphatic-aryl radical containing seven to nine carbon atoms, notably an alkaryl radical; and A is an anion, it being important that the R radial, where it is alkyl, contain not more than three carbon atoms and especially that it contain from one to two carbon atoms and, hence, that it be methyl or ethyl; that, except where is derived from a cyclic amine, as hereafter pointed out, the R, radical does not contain over three carbon atoms, and, in any event, that the maximum number of carbon atoms in R and R, does not exceed a total of four or five; and that, while R may contain a minimum of six of the aforesaid oxyalkylene, particularly oxypropylene groups, and may contain 40, 50 or 60 or even 100 or more of said groups, the minimum number of said groups be eight, with the preferred range being 8 to 25 or 30 of said groups, and an n being advantageously from 6 to 30 where the polyoxyalkylene radical is a polyoxypropylene radical.

As shown in U.S. Pat. No. 3,123,641, at least most of those of the particularly preferred quarternary ammonium type compounds which are derived from lower mono-alkyl amines can be represented by the formula (II) Re where R is an alkyl radical containing from one to three, and especially from one to two, carbon atoms, R, is

and R is where R is an alkyl radical containing from one to four carbon atoms, n and n are numbers the sum of which preferably does not exceed 60, the total number of carbon atoms in R, and R being at least 18; R is a hydrocarbon radical selected from the group consisting of alkyl and alkenyl radicals containing not more than four carbon atoms, or a lower aliphaticaromatic hydrocarbon radical containing from seven to nine carbon atoms; and A is an anion.

Various of those particularly preferred quaternary ammonium type compounds employed in the invention which are derived from lower dialkyl monoalkanolamines can be represented by the formula where R is an alkyl radical containing from one to three, and especially from one to two carbon atoms; R, is an alkyl radical containing from one to three carbon atoms; alkylene contains not more than three carbon atoms, R,-

is where R., is an alkyl radical containing from one to four carbon atoms, n is a number up to and preferably not exceeding 60, the total number of carbon atoms in R being at least 18; R is a hydrocarbon radical selected from the group consisting of alkyl and alkenyl radicals containing not more than four carbon atoms, or a lower aliphatic-aromatic hydrocarbon radical containing from seven to nine carbon atoms; and A is an anion.

Again, various of those of the particularly preferred quaternary ammonium type compounds used in the compositions of the present invention which are derived from lower monoalkyl dialkanolamines can be represented by the formula IV s Rg-O-alkylene A where R is an alkyl radical containing from one to three, and especially from one to two, carbon atoms, alkylene contains not more than three carbon atoms, R,0 is

andR is (V) R-O-alkylcne Ra R2 A and (VI) RO-alkylenc\ R;

R,-O-alkyleneN where alkylene contains not more than 3 carbon atoms, RO is in which R4 is an alkyl radical containing from one to four carbon atoms, n, n and nare numbers the sum of which preferably does not exceed 60, the total number of carbon atoms in R, R, and R being at least 18; R is a hydrocarbon radical selected from the group consisting of alkyl and alkenyl radicals containing not more than four carbon atoms, or a lower aliphaticaromatic hydrocarbon radical containing from seven to nine carbon atoms; and A is an anion.

Most of the quaternary ammonium type compounds having utility in the present invention fall into the category of or correspond to reaction products of quaternizing esters having a hydrocarbon alkyl or alkenyl radical containing not more than four carbon atoms, or a benzyl radical or a dimethylbenzyl radical or a lower alkylsubstituted or' chloror nitro-substituted benzyl radical, and an anion, with adducts of (a) aliphatic amines or cyclic amines containing a reactive hydrogen and a total of not more than six carbon atoms and in which no single aliphatic radical contains more than three carbon atoms, with (b) an a-epoxide containing at least three and advantageously from three to eight carbon atoms, the molal ratio of (a) to (b) being 1 of (a) to at least 6 of (b) when said a-epoxide contains three carbon atoms and ranging down to at least 2.5 of (b) when said a-epoxide contains eight carbon atoms.

Still others of the quaternary ammonium compounds that may be employed in the compositions of this invention can be represented by the formula Where R is an alkyl radical containing from one to three carbon atoms, R is an alkyl radical containing from one to three carbon atoms or is the same as R R is a polyoxyalkylene radical containing at least 18 carbon atoms and derived from an a-epoxide containing from three to eight carbon atoms, R is a hydroxy-alkyl radical containing from two to four carbon atoms and A is hydroxyl or other anion. Such compounds are readily :produced by reacting the adducts, such as those described in Examples a to v of US. Pat. No. 3,123,641, with ethyleneoxide in an aqueous medium in accordance with known quaternizing techniques. Typical of such compounds are those corresponding to the formulae where R is a polyoxypropylene or polyoxybutylene radical containing say from 6 to 30 oxypropylene or oxybutylene groups.

While, as indicated, many of the quaternary ammonium type compounds having utility for the purposes of this invention can be represented by the above formulae, they may, in general, best be described in the form of reaction products of identified ingredients, as hereafter pointed out. Thus, for example, quaternary ammonium compounds which are particularly useful are reaction products of quaternizing esters in the form of alkyl and alkenyl halides, sulfates and sulfonates containing from one to four carbon atoms, exemplified by methyl chloride, ethyl chloride, methyl chloracetate, and one and two carbon atom alkyl sulfates; or aromatic quaternizing esters in the form of halides, sulfates and sulfonates advantageously containing from seven to nine carbon atoms, exemplified by benzyl chlorides, dimethylbenzyl chloride, and phenylethyl chloride, with adducts of (0) alkyl amines having a reactive hydrogen and containing from one to four carbon atoms, such as dimethylamine and diethylamine with (b) propyleneoxide or butyleneoxides, said adducts containing 1 mol of (a) to from 6, and preferably from 8, to 30 mols of (b).

it is important to note that it is critical to the successful formulation of the compositions of the present invention that the oxyalkylene groups substituted on the quaternary ammonium type compounds be derived from an a-epoxide containing at least three carbon atoms. The most important embodiment of the a-epoxide whose use is contemplated herein in the production of the desired quaternary ammonium type compounds is propyleneoxide The a epoxides containing four, five, six or more carbon atoms can be used but, for general reasons of lack of economy or commercial availability, are not preferred. Typical of such latter a-epoxides are butyleneoxides such as l,2-butyleneoxide, pentylene epoxides, hexylene epoxides, heptylene epoxides, octylene epoxides, dodecylene epoxides, and C C, olefin oxides or epoxides, and, as well, styrene epoxide. It will be seen that most of those of the a-epoxides in which the vicinal carbons are terminal can conveniently by represented by the formula where R is an alkyl radical. In the case of propylene oxide, R is CH and in the representation of the group of propyleneoxide, butyleneoxides, pentyleneoxide and hexyleneoxide R contains from one to four carbon atoms. In the higher molecular weight alkylene oxides, R may contain as high as 16 carbon atoms.

While ethylene oxide cannot be employed as the sole alkylene oxide in preparing the quaternary ammonium cationic surfactants useful in preparing the novel anionic-cationic surfactant compositions of the present invention, minor proportions thereof, not to exceed about 20 percent by weight of the propylene oxide, or other a-epoxide employed, can be utilized as hereafter described. Mixtures of two or more of the a-epoxides containing at least three carbon atoms can, of course, be used as such, as well as in conjunction with ethylene oxide, subject to the limitation that the ethylene oxide must not exceed the aforesaid 20 percent of the weight of said a-epoxides.

The radical A can be any negative or salt-forming radical as, for instance, halogen such as chlorine, bromine and iodine; hydroxy; sulfate, alkyl-sulfuric acid such as methyl sulfuric acid or ethyl sulfuric acid (methosulfate of ethosulfate); nitrate; phosphate; acetate; formate; carbonate; lower alkyl (one to four carbon atoms) sulfonic acids; and the like. Of particular importance are those of the quaternary ammonium type compounds in which the anion is chlorine, bromine, methyl chloracetate, methosulfate, and ethosulfate. Various of said anionic radicals can be introduced directly into the molecules; and, in the case of others, they can be made, for instance, by substitution for halogen in the quaternary ammonium type compounds employed by known techniques as, for instance, by metathesis procedures.

The anionic surfactants which are compatible with the aforesaid quaternary ammonium compounds described herein, which mixtures form the novel compositions of the present invention, comprise a broad spectrum of compounds, as is well known to those skilled in the art. Members of this classification comprise the water-soluble salts such as the alkali metal and amine soaps of straight and branched chain fatty acids, said fatty acids being both naturally occurring, such as from coconut oil or from tall oil, and synthetically produced such as by paraffin oxidation; the water soluble salts of organic sulfonic acids, alkyl sulfuric acids and sulfuric acid esters of polyhydric alcohols incompletely esterified with a fatty acid of high molecular weight, sulfated and sulfonated higher fatty acid amides and alkanolamides which include the sulfated fatty oil, sulfated fatty acids, sulfated straight chain and branched chain C -C alcohols, sulfated alkylolamides and the like. The more important of this group are the alkyl sulfates prepared by reacting a fatty alcohol with sulfuric acid or chlorosulfonic acid, said fatty alcohol having from about eight to 18 carbon atoms, of particular utility in preparing the compositions of the present invention being the alkali metal, alkaline earth metal, ammonium, lower amine and a1- kanolamine alkyl sulfates wherein the alkyl group contains from eight to 18 carbon atoms.

Other compatible anionic surfactants useful in preparing the compositions of the present invention are the alkanesulfonates, esterand ether-linked sulfonates such as the di-alkyl sulfo-succinates, amide linked sulfonates and various derivatives thereof. Also suitable are the well known alkylaryl sulfonates, both straight and branched chain, sodium dodecylbenzene sulfonate being the common commercial product. These alkylaryl sulfonates usually contain from about six to 26 carbon atoms in the alkyl chain. The aforesaid alkylaryl sulfonates may also contain intermediate linkages such as amide and hydrazide linkages, as exemplified by the sulfonated a-alkylbenzimidazoles, and ester and ether linkages. Further types of suitable anionic surfactants are the esters of the oxy acids of phosphorous with aliphatic alcohols having from about six to 18 carbon atoms and alkyl phenols wherein the alkyl chain contains from eight to 18 carbon atoms.

Especially suitable and preferred are anionic detergents wherein the anionic surfactant solubilizing group is a member selected from the group consisting of SO H, SO H, COOH and the water-soluble salts thereof especially the alkali metal, alkaline earth metal, ammonium and lower amine and alkanolamine salts.

The anionic surfactants are disclosed in numerous patents among which may be mentioned, by way of illustration, U.S. Pat. Nos. 2,383,737; 2,486,921; 2,920,045; and 3,004,056.

Broadly speaking, the aforesaid quaternary ammonium surfactant may be combined with the aforesaid anionic surfactants over a wide range of proportions, since the compatibility is not limited by any critical weight proportions, and there will be no significant diminution of surface active properties, no matter what the ratio of the said surfactants may be to each other. Preferably, in order to realize the foam boosting effect of the combination of anionic surfactant and the aforesaid quaternary ammonium surfactant, there is employed from about 20 to 40 percent, better still about 25 to 30 percent, of said quaternary ammonium surfactant, based on the weight of combined cationic and anionic surfactants in the compositions.

The following examples are illustrative of the practice of the present invention but are not to be considered as limitativc of its scope.

EXAMPLE 1 The following tabulated data represent the results of the Shake Foam Test (50 mls total liquid in 250 ml cylinder, 20 inversions). The anionic surfactant employed was sodium lauryl sulfate; the cationic surfactant was a quaternary ammonium compound of the formula Cg: Cal-I /1 CH3 R Cl but a cationic surfactant similar to that in Example 1 was employed except the polyoxypropylene radical contained about 30 oxypropylene groups.

TABLE 2 Shake Foam Test Foam Height Conc. Conc. Hard Water Anionic Cationic (342 p.p.m.)

EXAMPLE 3 The shake foa'm test was repeated with the cationic surfac- 40 tant of Example 1 and the triethanolamine salt of dodecylbenzene sulfonic acid as the anionic surfactant.

TABLE 3 Shake Foam Test Foam Height Conc. Conc. Distilled Hard Water Anionic Cationic Water (342p.p.m.)

EXAMPLE 4 The Shake Foam Test was repeated utilizing coconut oil soap as the anionic surfactant and the cationic surfactant of TABLE 1 Shake Foam Test Foam Height Conc. Conc. Distilled Hard Water Anionic Cationic Water 342p.p.m.

Example 1:

TABLE 4 Shake Foam Test Foam Height Conc. Anionic Conc. Cationic Distilled Water EXAMPLE An illustrative liquid shampoo formulation utilizing an illustrative cationic quaternary ammonium compound described herein with an illustrative anionic surfactant is given below.

'l'riethanulaminc lauryl sulfate [5% Lnnolin 2% Uleyl Alcohol l% llcxachlorophene 1% Propoxylutud Quaternary 8% Water 73% Compound formed by quaternizing a condensation product of 1 mol of diethyl ethanolamine and 25 moles of propyleneoxide with methyl chloride. Here the quaternary acts simultaneously as a surfactant, foam boosting agent and solubilizer for hexachlorophene.

Additional illustrative examples of compositions made in accordance with the present invention are as follows, the pro portions stated being in weight percent.

EXAMPLE 6 Phosphate ester of [0 mol ethylene oxide adduct of nonyl phenol (sodium salt) 25 mol propylene oxide adduct of dimethylamine quaternized with ethyl chloride EXAMPLE 7 Phosphate ester of 12 mol ethylene oxide adduct of dodecyl alcohol (triethanolamine salt) 16 mol propylene oxide adduct of methylethylamine quaternized with benzyl chloride EXAMPLE 8 Laurie acid monoester of sulfuric acid monoester of glycerol (triethanolamine salt) 18 mol propylene oxide adduct of dimethylethanolamine quatemized with methyl chloracetate EXAMPLE 9 Sodium lauryl sulfate 70% 12 mol butylene oxide adduct of dimethylamine quaternized with dimethyl sulfate wherein R is alkyl containing from one to three carbon atoms, R, is a member selected from the group consisting of alkyl containing from one to three carbon atoms and and compounds wherein R and R are joined together to form with the N atom a member of the group consisting of piperidine, methyl piperidine and pyrrolidiene; R is where R, is alkyl containing from one to four carbon atoms, n and n are numbers the sum of which does not exceed 60, the total number of carbon atoms in R, being at least 18; R is a member selected from the group consisting of alkyl and alkenyl containing from one to four carbon atoms; benzene; methyl benzenes; ethyl benzenes;

and their methyl and ethyl nuclearly substituted derivatives; and the mono-halo mono-nitro nuclearly substituted derivatives of the foregoing; and A is an anion.

2. A composition according to claim 1 wherein the anionic surfactant is selected from the group consisting of alkyl sulfates, alkylaryl sulfonates and fatty carboxylic acid soaps 3. A composition according to claim 2 wherein the anionic surfactant is an alkali metal alkyl sulfate wherein the alkyl group contains from eight to 18 carbon atoms.

4. A composition according to claim 2 wherein the anionic surfactant is an alkali metal alkyl benzene sulfonate wherein the alkyl group contains from eight to 18 carbon atoms.

5. A composition according to claim 1 in which the R radical of said cationic surfactant compound contains a polyoxyethylene radical in which the ethylene oxide constitutes not more than 20 percent by weight of said R radical.

6. A composition according to claim 1 in which the R and R radicals of said quaternary ammonium compound are joined together to form with the N atom a cyclic amine containing not more than six carbon atoms, with the proviso that the total number of carbon atoms in R and R does not exceed 6; and R is polyoxyalkylene containing at least 18 carbon atoms and derived from an a-epoxide containing from three to six carbon atoms.

7. A composition consisting essentially of a water-soluble anionic surfactant being a member selected from the group consisting of fatty acid soaps, alkyl sulfates, sulfates of polyhydric alcohols partially esterified with a fatty acid, sulfated and sulfonated fatty acid amides and alkanolamides, alkane-sulfonates, ester-, etherand amide-linked sulfonates, alkylaryl sulfonates and phosphates of aliphatic alcohols and alkyl phenols and from about 20 to 40 percent by weight of a cationic surfactant, based on the weight of combined cationic and anionic surfactants, corresponding to the formula where R is alkyl containing from one to three carbon atoms, R, is

CH CH-O- 2' I 1&4 n

and R is where R is alkyl containing from one to four carbon atoms, n and n are numbers the sum of which does not exceed 60, the total number of carbon atoms in R, and R being at least 18; R is a member selected from the group consisting of l alkyl and alkenyl containing not more than four carbon atoms, and (2)benzene; methyl benzenes', ethyl benzenes;

alkylaryl sulfonates and phosphates of aliphatic alcohols and 10 alkyl phenols and from about 20 to 40 percent by weight of a cationic surfactant, based on the weight of combined cationic and anionic surfactants, corresponding to the formula where R is alkyl containing from one to three carbon atoms, R is alkyl containing from one to three carbon atoms, alkylenc contains not more than three carbon atoms, R is where R, is alkyl containing from one to four carbon atoms, n is a number up to and including 60, the total number of carbon atoms in R being at least 18; R-; is a member selected from the group consisting of (1) alkyl and alkenyl containing not more than four carbon atoms, and (2) benzene; methyl benzenes; ethyl benzenes:

and their methyl and ethyl nuclearly substituted derivatives; and the mono-halo and mono-nitro nuclearly substituted derivatives of the foregoing; and A is an innocuous anion.

9. A composition consisting essentially of a water-soluble I anionic surfactant being a member selected from the group consisting of fatty acid soaps, alkyl sulfates sulfates of polyhydric alcohols partially esterified with a fatty acid, sulfated and sulfonated fatty acid amides and alkanolamides, alkane-sulfonates, ester-, etherand amide-linked sulfonates, alkylaryl sulfonates and phosphates of aliphatic alcohols and alkyl phenols and from about 20 to 40 percent by weight of a cationic surfactant, based on the weight of combined cationic and anionic surfactants, corresponding to the formula where R is alkyl containing from one to three carbon atoms, alkylene contains not more than three carbon atoms, R,-0 is and their methyl and ethyl nuclearly substituted derivatives; and the mono-halo and mono-nitro nuclearly substituted derivatives of the foregoing; and A is an innocuous anion.

10. A composition consisting essentially of a water-soluble anionic surfactant being a member selected from the group consisting of fatty acid soaps, alkyl sulfates, sulfates of polyhydric alcohols partially esterified with a fatty acid, sulfated and sulfonated fatty acid amides and alkanolamides, alkane-sulfonates, ester-, etherand amide-linked sulfonates, alkylaryl sulfonates and phosphates of aliphatic alcohols and alkyl phenols and from about 20 to 40 percent by weight of a cationic surfactant, based on theweight of combined cationic and anionic surfactants, corresponding to the formula where alkylene contains not more than three carbon atoms,

in which R is alkyl containing from one to four carbon atoms, n, n and n are numbers the sum of which does not exceed 60, the total number of carbon atoms in R, R and R being at least 18; R is a member selected from the group consisting of 1) alkyl and alkenyl containing not more than four carbon atoms, and (2)benzene; methyl benzenes; ethyl benzenes;

and their methyl and ethyl nuclearly substituted derivatives; and the mono-halo and mono-nitro nuclearly substituted derivatives of the foregoing; and A is an innocuous anion.

11. A composition consisting essentially of a water-soluble anionic surfactant being a member selected from the group consisting of fatty acid soaps, alkyl sulfates, sulfates of polyhydric alcohols partially esterified with a fatty acid, sulfated and sulfonated fatty acid amides and alkanolamides, alkane-sulfonates, ester-, etherand amide-linked sulfonates, alkylaryl sulfonates and phosphates of aliphatic alcohols and alkyl phenols and from about 20 to 40 percent by weight of a cationic surfactant, based on the weight of combined cationic and anionic surfactants, corresponding to the formula where R is alkyl containing from one to three carbon atoms, R is selected from the group consisting of alkyl containing from one to three carbon atoms and hydroxyalkyl containing from two to four carbon atoms, R, is a polyoxyalkylene substituent containing at least 18 carbon atoms and derived from an a-epoxide containing from three to eight carbon atoms, R is a member selected from the group consisting of 1 a hydroxyalkyl containing from two to four carbon atoms, and (2) benzene; methyl benzenes; ethyl benzenes;

polyhydric alcohols partially esterified with a fatty acid,

sulfated and sulfonated fatty acid amides and alkanolamides, alkane-sulfonates, ester-, etherand amide-linked sulfonates, alkylaryl sulfonates and phosphates of aliphatic alcohols and alkyl phenols and from about to 40 percent by weight of a cationic surfactant, based on the weight of combined cationic and anionic surfactants, corresponding to the formula where alkylene contains not more than three carbon atoms, R-O- R1 is and R is and their methyl and ethyl nuclearly substituted derivatives; and the mono-halo and mono-nitro nuclearly substituted derivatives of the foregoing; and A is an innocuous anion.

13. A composition consisting essentially of a water insoluble anionic surfactant being a member selected from the group consisting of fatty acid soaps, alkyl sulfates, sulfates of polyhydric alcohols partially esterified with a fatty acid, sulfated and sulfonated fatty acid amides and alkanolamides, alkane-sulfonates, ester-, ether and amide-linked sulfonates, alkylaryl sulfonates and phosphates of aliphatic alcohols and alkyl phenols and from about 20 to 40 percent by weight of a cationic surfactant, based on the weight of combined cationic and anionic surfactants, corresponding to the formula one to four carbon atoms, n total number of carbon where R, is alkyl containing from is a number up to and including 60, the

atoms is R; being at least 18, v is a number at least 1 with the proviso that the weight ratio of (C Ht0-), to R is not greater than one to four, X is a member selected from the group consisting of (l alkyl and alkenyl containing from one to four carbon atoms, and (2) benzene; lower alkyl benzenes in which the lower alkyl contain from one to four carbon and their methyl and ethyl nuclearly substituted derivatives;

and the mono-halo, mono-nitro and mono-sulfonic nuclearly substituted derivatives of the foregoing; and A is an anion.

14. A composition consisting essentially of a water-soluble anionic surfactant being a member selected from the group consisting of fatty acid soaps, alkyl sulfates, sulfates of polyhydric alcohols partially esterified with a fatty acid, sulfated and sulfonated fatty acid amides and alkanolamides, alkane' sulfonates, ester-, etherand amide-linked sulfonates, alkylaryl sulfonates and phosphates of aliphatic alcohols and lakyl phenols and from about 20 to alkyl percent by weight of a cationic surfactant, based on the weight of combined cationic and anionic surfactants, corresponding to the formula A C2H4 0' )v 2 where R is alkyl containing from one to three carbon atoms, R, is

where R is alkyl containing from one to four carbon atoms, n is a number up to and including 60, the total number of carbon atoms in R being at least 18, v is a number at least 1 with the proviso that the weight ratio of (C H -O-),. to R is not greater than one to four, X is a member selected from the group consisting of l alkyl and alkenyl containing from one to four carbon atoms, and benzene; lower alkyl benzenes in which the lower alkyls contain from one to four carbon atoms,

and their methyl and ethyl nuclearly substituted derivatives; and the mono-halo, mono-nitro and mono-sulfonic nuclearly substituted derivatives of the foregoing; and A is an anion.

15 A composition consisting essentially of a water-soluble anionic surfactant being a member selected from the group consisting of fatty acid soaps, alkyl sulfates, sulfates of polyhydric alcohols partially esterified with a fatty acid, sulfated and sulfonated fatty acid amides and alkanolamides, alkane-sulfonates, ester-, etherand amide linked sulfonates, alkylaryl sulfonates and phosphates of aliphatic alcohols and alkyl phenols and from about 20 to 40 percent by weight of a cationic surfactant, based on the weight of combined cationic and anionic surfactants, corresponding to the formula where R and R are the same or dissimilar alkyls each containing from 1 to 3 carbon atoms, R,-O-R is polyoxyethylenepolyoxypropylene containing at least 6 oxypropylene groups and where the weight ratio of the polyoxyethylene to the polyoxypropylene is not greater than one to four, the total number of oxypropylene groups not exceeding 60, X is a member selected from the group consisting of l alkyl and al- IOIO39 0178 kenyl containing from one four carbon atoms, and (2) benzene; lower alkyl benzenes in which the lower alkyls contain from one to four carbon atoms,

alkyl phenols and from about to 40 percent bysweight of a cationic surfactant, based on the weight of combined cationic and anionic surfactants, corresponding to the formula where R is alkyl containing from one to three carbon atoms, R,OR is polyoxyethylene-polyoxypropylene containing at least 6 oxypropylene groups and where the weight ratio of the polyoxyethylene to the polyoxypropylene is not greater than one to four, the total number of oxypropylene groups not exceeding 60, X is a member selected from the group consisting of 1) alkyl and alkenyl containing from one to four carbon atoms, and benzene; lower alkyl benzenes in which the lower alkyls contain from one to four carbon atoms,

and their methyl and ethyl nuclearly substituted derivatives; and the monohalo, mono-nitro and mono-sulfonic nuclearly substituted derivatives of the foregoing; and A is an anion.

17. A composition consisting essentially of a water-soluble anionic surfactant being a member selected from the group consisting of fatty acid soaps, alkyl sulfates, sulfates of polyhydric alcohols partially esterified with a fatty acid, sulfated and sulfonated fatty acid amides and alkanolamides, alkane-sulfonates, ester-, etherand amide-linked sulfonates, alkylaryl sulfonates and phosphates of aliphatic alcohols and alkyl phenols and from about 20 to 40 percent by weight of a cationic surfactant, based on the weight of combined cationic and anionic surfactants, corresponding to the formula where R is an alkyl containing from one to three carbon atoms R is greater than one to four, X is a member selected from the group consisting of 1) alkyl and alkenyl containing from one to four carbon atoms, and (2) benzene; lower alkyl benzenes in which the lower alkyls contain from one to four carbon atoms,

and their methyl and ethyl nuclearly substituted derivatives; and the mono-halo, mono-nitro and mono-sulfonic nuclearly substituted derivatives of the foregoing; and A is an anion.

18. A composition consisting essentially of a water-soluble anionic surfactant being a member selected from the group consisting of fatty acid soaps, alkyl sulfates, sulfates of polyhydric alcohols partially esterified with a fatty acid, sulfated and sulfonated fatty acid amides and alkanolamides, alkane-sulfonates, ester-, etherand amide-linked sulfonates, alkylaryl sulfonates and phosphates of aliphatic alcohols and alkyl phenols and from about 20 to 40 percent by weight of a cationic surfactant, based on the weight of combined cationic and anionic surfactants, corresponding to the formula where R is alkyl containing from one to three carbon atoms,

R is

and their methyl and ethyl nuclearly substituted derivatives; and the mono-halo, mono-nitro and mono-sulfonic nuclearly substituted derivatives of the foregoing; and A is an anion.

19. A composition consisting essentially of a water-soluble anionic surfactant being a member selected from the group consisting of fatty acid soaps, alkyl sulfates, sulfates of polyhydric alcohols partially esterified with a fatty acid, sulfated and sulfonated fatty acid amides and alkanolamides, alkane-sulfonates, ester-, etherand amide-linked sulfonates, alkylaryl sulfonates and phosphates of aliphatic alcohols and alkyl phenols and from about 20 to 40 percent by weight of a cationic surfactant, based on the weight of combined cationic and anionic surfactants, corresponding to the formula where R is alkyl containing from one to three carbon atoms, R alkyl containing from one to three carbon atoms, R is and n totals a number from 8 to 30, X is a member selected from the group consisting of 1) alkyl and alkenyl containing from one to four carbon atoms, and (2) benzene; lower alkyl benzenes in which the lower alkyls contain from one to four carbon atoms,

and their methyl and ethyl nuclearly substituted derivatives; and the mono-halo, mono-nitro and mono-sulfonic nuclearly substituted derivatives of the foregoing; and A is an anion.

20. A composition consisting essentially of a water-soluble anionic surfactant being a member selected from the group consisting of fatty acid soaps, alkyl sulfates, sulfates of polyhydric alcohols partially esterified with a fatty acid, sulfated and sulfonated fatty acid amides and alkanolamides, alkane-sulfonates, ester-, etherand amide-linked sulfonates, alkylaryl sulfonates and phosphates of aliphatic alcohols and alkyl phenols and from about 20 to 40 percent, by weight of a cationic surfactant, based on the weight of combined cationic and anionic surfactants, corresponding to the formula and R is alkyl containing from one to four carbon atoms, and n totals a number not exceeding 60 with the proviso that the number of carbon atoms in the total of the R, radicals is at least 18, v is a number at leat l with the proviso that the weight ratio of (C,l-l,--O) to R, is not greater than one to four, X is a member selected from the group consisting of l alkyl and alkenyl containing from one to four carbon atoms, and (2) benzene; lower alkyl benzenes in which the lower alkyls contain from one to four carbon atoms,

and their methyl and ethyl nuclearly substituted derivatives; and the mono-halo, mono-nitro and mono-sulfonic nuclearly substituted derivatives of the foregoing; and A is an anion. 

2. A composition according to claim 1 wherein the anionic surfactant is selected from the group consisting of alkyl sulfates, alkylaryl sulfonates and fatty carboxylic acid soaps.
 3. A composition according to claim 2 wherein the anionic surfactant is an alkali metal alkyl sulfate wherein the alkyl group contains from eight to 18 carbon atoms.
 4. A composition according to claim 2 wherein the anionic surfactant is an alkali metal alkyl benzene sulfonate wherein the alkyl group contains from eight to 18 carbon atoms.
 5. A composition according to claim 1 in which the R2 radical of said cationic surfactant compound contains a polyoxyethylene radical in which the ethylene oxide constitutes not more than 20 percent by weight of said R2 radical.
 6. A composition according to claim 1 in which the R and R1 radicals of said quaternary ammonium compound are joined togeTher to form with the N atom a cyclic amine containing not more than six carbon atoms, with the proviso that the total number of carbon atoms in R and R1 does not exceed 6; and R2 is polyoxyalkylene containing at least 18 carbon atoms and derived from an Alpha -epoxide containing from three to six carbon atoms.
 7. A composition consisting essentially of a water-soluble anionic surfactant being a member selected from the group consisting of fatty acid soaps, alkyl sulfates, sulfates of polyhydric alcohols partially esterified with a fatty acid, sulfated and sulfonated fatty acid amides and alkanolamides, alkane-sulfonates, ester-, ether- and amide-linked sulfonates, alkylaryl sulfonates and phosphates of aliphatic alcohols and alkyl phenols and from about 20 to 40 percent by weight of a cationic surfactant, based on the weight of combined cationic and anionic surfactants, corresponding to the formula
 8. A composition consisting essentially of a water-soluble anionic surfactant being a member selected from the group consisting of fatty acid soaps, alkyl sulfates, sulfates of polyhydric alcohols partially esterified with a fatty acid, sulfated and sulfonated fatty acid amides and alkanolamides, alkane-sulfonates, ester-, ether- and amide-linked sulfonates, alkylaryl sulfonates and phosphates of aliphatic alcohols and alkyl phenols and from about 20 to 40 percent by weight of a cationic surfactant, based on the weight of combined cationic and anionic surfactants, corresponding to the formula
 9. A composition consisting essentially of a water-soluble anionic surfactant being a member selected from the group consisting of fatty acid soaps, alkyl sulfates sulfates of polyhydric alcohols partially esterified with a fatty acid, sulfated and sulfonated fatty acid amides and alkanolamides, alkane-sulfonates, ester-, ether- and amide-linked sulfonates, alkylaryl sulfonates and phosphates of aliphatic alcohols and alkyl phenols and from about 20 to 40 percent by weight of a cationic surfactant, based on the weight of combined cationic and anionic surfactants, corresponding to the formula
 10. A composition consisting essentially of a water-soluble anionic surfactant being a member selected from the group consisting of fatty acid soaps, alkyl sulfates, sulfates of polyhydric alcohols partially esterified with a fatty acid, sulfated and sulfonated fatty acid amides and alkanolamides, alkane-sulfonates, ester-, ether- and amide-linked sulfonates, alkylaryl sulfonates and phosphates of aliphatic alcohols and alkyl phenols and from about 20 to 40 percent by weight of a cationic surfactant, based on the weight of combined cationic and anionic surfactants, corresponding to the formula
 11. A composition consisting essentially of a water-soluble anionic surfactant being a member selected from the group consisting of fatty acid soaps, alkyl sulfates, sulfates of polyhydric alcohols partially esterified with a fatty acid, sulfated and sulfonated fatty acid amides and alkanolamides, alkane-sulfonates, ester-, ether- and amide-linked sulfonates, alkylaryl sulfonates and phosphates of aliphatic alcohols and alkyl phenols and from about 20 to 40 percent by weight of a cationic surfactant, based on the weight of combined cationic and anionic surfactants, corresponding to the formula
 12. A composition consisting essentially of a water-soluble anionic surfactant being a member selected from the group consisting of fatty acid soaps, alkyl sulfates, sulfates of polyhydric alcohols partially esterified with a fatty acid, sulfated and sulfonated fatty acid amides and alkanolamides, alkane-sulfonates, ester-, ether- and amide-linked sulfonates, alkylaryl sulfonates and phosphates of aliphatic alcohols and alkyl phenols and from about 20 to 40 percent by weight of a cationic surfactant, based on the weight of combined cationic and anionic surfactants, corresponding to the formula
 13. A composition consisting essentially of a water insoluble anionic surfactant being a member selected from the group consisting of fatty acid soaps, alkyl sulfates, sulfates of polyhydric alcohols partially esterified with a fatty acid, sulfated and sulfonated fatty acid amides and alkanolamides, alkane-sulfonates, ester-, ether- and amide-linked sulfonates, alkylaryl sulfonates and phosphates of aliphatic alcohols and alkyl phenols and from about 20 to 40 percent by weight of a cationic surfactant, based on the weight of combined cationic and anionic surfactants, corresponding to the formula where R and R1 are the same or dissimilar alkyls each containing from one to three carbon atoms, R2 is where R3 is alkyl containing from one to four carbon atoms, n is a number up to and including 60, the total number of carbon atoms is R2 being at least 18, v is a number at least 1 with the proviso that the weight ratio of (C2H4-0-)v to R2 is not greater than one to four, X is a member selected from the group consisting of (1) alkyl and alkenyl containing from one to four carbon atoms, and (2) benzene; lower alkyl benzenes in which the lower alkyl contain from one to four carbon atoms, and their methyl and ethyl nuclearly substituted derivatives; and the mono-halo, mono-nitro and mono-sulfonic nuclearly substituted derivatives of the foregoing; and A is an anion.
 14. A composition consisting essentially of a water-soluble anionic surfactant being a member selected from the group consisting of fatty acid soaps, alkyl sulfates, sulfates of polyhydric alcohols partially esterified with a fatty acid, sulfated and sulfonated fatty acid amides and alkanolamides, alkane-sulfonates, ester-, ether- and amide-linked sulfonates, alkylaryl sulfonates and phosphates of aliphatic alcohols and lakyl phenols and from about 20 to alkyl percent by weight of a cationic surfactant, based on the weight of combined cationic and anionic surfactants, corresponding to the formula where R is alkyl containing from one to three carbon atoms, R2 is where R3 is alkyl containing from one to four carbon atoms, n is a number up to and including 60, the total number of carbon atoms in R2 being at least 18, v is a number at least 1 with the proviso that the weight ratio of (C2H4-O-)v to R2 is not greater than one to four, X is a member selected from the group consisting of (1) alkyl and alkenyl containing from one to four carbon atoms, and benzene; lower alkyl benzenes in which the lower alkyls contain from one to four carbon atoms, and their methyl and ethyl nuclearly substituted derivatives; and the mono-halo, mono-nitro and mono-sulfonic nuclearly substituted derivatives of the foregoing; and A is an anion.
 15. A composition consisting essentially of a water-soluble anionic surfactant being a member selected from the group consisting of fatty acid soaps, alkyl sulfates, sulfates of polyhydric alcohols partially esterified with a fatty acid, sulfated and sulfonated fatty acid amides and alkanolamides, alkane-sulfonates, ester-, ether- and amide-linked sulfonates, alkYlaryl sulfonates and phosphates of aliphatic alcohols and alkyl phenols and from about 20 to 40 percent by weight of a cationic surfactant, based on the weight of combined cationic and anionic surfactants, corresponding to the formula where R and R1 are the same or dissimilar alkyls each containing from 1 to 3 carbon atoms, R4-O-R5 is polyoxyethylene-polyoxypropylene containing at least 6 oxypropylene groups and where the weight ratio of the polyoxyethylene to the polyoxypropylene is not greater than one to four, the total number of oxypropylene groups not exceeding 60, X is a member selected from the group consisting of (1) alkyl and alkenyl containing from one four carbon atoms, and (2) benzene; lower alkyl benzenes in which the lower alkyls contain from one to four carbon atoms, and their methyl and ethyl nuclearly substituted derivatives; and the mono-halo, mono-nitro and mono-sulfonic nuclearly substituted derivatives of the foregoing; and A is an anion.
 16. A composition consisting essentially of a water-soluble anionic surfactant being a member selected from the group consisting of fatty acid soaps, alkyl sulfates, sulfates of polyhydric alcohols partially esterified with a fatty acid, sulfated and sulfonated fatty acid amides and alkanolamides. alkane-sulfonates, ester-, ether- and amide-linked sulfonates, alkylaryl sulfonates and phosphates of aliphatic alcohols and alkyl phenols and from about 20 to 40 percent by weight of a cationic surfactant, based on the weight of combined cationic and anionic surfactants, corresponding to the formula where R is alkyl containing from one to three carbon atoms, R4-O-R5 is polyoxyethylene-polyoxypropylene containing at least 6 oxypropylene groups and where the weight ratio of the polyoxyethylene to the polyoxypropylene is not greater than one to four, the total number of oxypropylene groups not exceeding 60, X is a member selected from the group consisting of (1) alkyl and alkenyl containing from one to four carbon atoms, and benzene; lower alkyl benzenes in which the lower alkyls contain from one to four carbon atoms, and their methyl and ethyl nuclearly substituted derivatives; and the mono-halo, mono-nitro and mono-sulfonic nuclearly substituted derivatives of the foregoing; and A is an anion.
 17. A composition consisting essentially of a water-soluble anionic surfactant being a member selected from the group consisting of fatty acid soaps, alkyl sulfates, sulfates of polyhydric alcohols partially esterified with a fatty acid, sulfated and sulfonated fatty acid amides and alkanolamides, alkane-sulfonates, ester-, ether- and amide-linked sulfonates, alkylaryl sulfonates and phosphates of aliphatic alcohols and alkyl phenols and from about 20 to 40 percent by weight of a cationic surfactant, based on the weight of combined cationic and anionic surfactants, corresponding to the formula where R is an alkyl containing from one to three carbon atoms R2 is
 18. A composition consisting essentially of a water-soluble anionic surfactant being a member selected from the group consisting of fatty acid soaps, alkyl sulfates, sulfates of polyhydric alcohols partially esterified with a fatty acid, sulfated and sulfonated fatty acid amides and alkanolamides, alkane-sulfonates, ester-, ether- and amide-linked sulfonates, alkylaryl sulfonates and phosphates of aliphatic alcohols and alkyl phenols and from about 20 to 40 percent by weight of a cationic surfactant, based on the weight of combined cationic and anionic surfactants, corresponding to the formula where R is alkyl containing from one to three carbon atoms, R2 is and n totals a number from 8 to 30, X is a member selected from the group consisting of (1) alkyl and alkenyl containing from one to four carbon atoms, and (2) benzene; lower alkyl benzenes in which the lower alkyls contain from one to four carbon atoms, and their methyl and ethyl nuclearly substituted derivatives; and the mono-halo, mono-nitro and mono-sulfonic nuclearly substituted derivatives of the foregoing; and A is an anion.
 19. A composition consisting essentially of a water-soluble anionic surfactant being a member selected from the group consisting of fatty acid soaps, alkyl sulfates, sulfates of polyhydric alcohols partially esterified with a fatty acid, sulfated and sulfonated fatty acid amides and alkanolamides, alkane-sulfonates, ester-, ether- and amide-linked sulfonates, alkylaryl sulfonates and phosphates of aliphatic alcohols and alkyl phenols and from about 20 to 40 percent by weight of a cationic surfactant, based on the weight of combined cationic and anionic surfactants, corresponding to the formula where R is alkyl containing from one to three carbon atoms, R2 alkyl containing from one to three carbon atoms, R2 is and n totals a number from 8 to 30, X is a member selected from the group consisting of (1) alkyl and alkenyl containing from one to four carbon atoms, and (2) benzene; lower alkyl benzenes in which the lower alkyls contain from one to four carbon atoms, and their methyl and ethyl nuclearly substituted derivatives; and the mono-halo, mono-nitro and mono-sulfonic nuclearly substituted derivatives of the foregoing; and A is an anion.
 20. A composition consisting essentially of a water-soluble anionic surfactant being a member selected from the group consisting of fatty acid soaps, alkyl sulfates, sulfates of polyhydric alcohols partially esterified with a fatty acid, sulfated and sulfonated fatty acid amides and alkanolamides, alkane-sulfonates, ester-, ether- and amide-linked sulfonates, alkylaryl sulfonates and phosphates of aliphatic alcohols and alkyl phenols and from about 20 to 40 percent, by weight of a cationic surfactant, based on the weight of combined cationic and anionic surfactants, corresponding to the formula 